Classifications

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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
  • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
  • B01J31/188—Amide derivatives thereof
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  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
  • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
  • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
  • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
  • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
  • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
  • C07C2/08—Catalytic processes
  • C07C2/26—Catalytic processes with hydrides or organic compounds
  • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/20—Olefin oligomerisation or telomerisation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
  • B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
  • B01J2531/62—Chromium
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/842—Iron
• • C—CHEMISTRY; METALLURGY
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  • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • C07C2531/22—Organic complexes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1088—Olefins
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/70—Catalyst aspects
  • C10G2300/703—Activation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/20—C2-C4 olefins
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/22—Higher olefins
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• This invention relates to the oligomerisation of olefinic compounds in the presence of both a tetramerisation catalyst and a further oligomerisation catalyst to produce a mixture of tetramers and other oligomers.
• a tetramerisation reaction as described in PCT/ZA2003/000187 and PCT/ZA2003/000186 can be combined with at least one further oligomerisation reaction to yield a mixture of tetramers and other oligomers.
• the processes described in PCT/ZA2003/000187 and PCT/ZA2003/000186 also yield a somewhat mixed oligomerised product, the ratios between the oligomers being dependant on and determined by the catalyst system and reaction conditions selected.
• the current process can now be used to manipulate the ratios of the oligomers in the product stream as may be required by market needs.
• a tetramerisation reaction as described in this patent application is compatible with a further oligomerisation reaction and accordingly is suitable to manipulate the composition of the oligomerised product stream.
• a process for the oligomerisation of at least one olefinic compound in the form of an olefin or a compound including an olefinic moiety by contacting the at least one olefinic compound with at least two different catalysts, namely a tetramerisation catalyst and a further oligomerisation catalyst, wherein the tetramerisation catalyst comprises a combination of i) a source of a transition metal; and ii) a ligating compound of the formula
• X 1 and X 2 are independently selected from the group consisting of N, P, As, Sb, Bi, O, S and Se ;
• Y is a linking group between X 1 and X 2 ;
• m and n are independently 0, 1 or a larger integer; and
• R 1 and R 2 are independently hydrogen, a hydrocarbyl group, or a heterohydrocarbyl group, and R 1 being the same or different when m>1 , and R 2 being the same or different when n>1 , provided that (a) if two or more of R 1 and R 2 are aromatic with a ring atom of the aromatic ring structure bound to either X 1 or X 2 , not more than two of said aromatic R 1 and R 2 have a substituent as a non-ring atom bound to a ring atom of the aromatic ring structure adjacent to the ring atom bound to X 1 or X 2 ; and (b) none of R 1 and R 2 are aromatic with a ring atom of the aromatic
• a substituent is a moiety (excluding H) which is bound to a linear structure or a cyclic structure bound to X 1 and X 2 , but does not form part of the linear or cyclic structure.
• a polar substituent is a substituent with a permanent electric or induced dipole moment.
• the source of transition metal is a source of a Group IV to VI transition metal.
• it is a source of Cr, Ti, V, Ta or Zr.
• it is a source of either Cr, Ta or Ti.
• the source of the Group IV to VI transition metal may be an inorganic salt, an organic salt, a coordination compound or an organometallic complex.
• the source of transition metal is a source of chromium and preferably it is selected from the group consisting of chromium trichloride tris-tetrahydrofuran complex; (benzene)tricarbonyl chromium; chromium (111) octanoate; chromium hexacarbonyl; chromium (III) acetylacetonate and chromium (III) 2- ethylhexanoate.
• it is chromium (III) acetylacetonate.
• X 1 and/or X 2 may be a potential electron donor for coordination with the transition metal.
• An electron donor is defined as an entity that donates electrons used in chemical, including dative covalent, bond formation.
• X 1 and/or X 2 may be independently oxidised by S, Se, N or O.
• X 1 and/or X 2 may be independently phosphorus or phosphorus oxidised by S or Se or N or O.
• X 1 and X 2 are the same, and preferably both are P.
• m and n are dependent on factors such as the valence and oxidation state of X 1 and X 2 , bond formation of Y with X 1 and X 2 respectively, and bond formation of R* and R 2 with X 1 and X 2 respectively.
• both m an n are not 0.
• the ligating compound is of the formula
• Y is as defined above;
• X 1 and X 2 are independently selected from the group consisting of N, P, As, Sb and Bi; and R 3 to R 6 are the same or different and are each independently a hydrocarbyl group or a heterohydrocarbyl group, provided that (a) if two or more of R 3 to R 6 are aromatic with a ring atom of the aromatic ring structure bound to either X 1 or X 2 not more than two of said aromatic R 3 to R 6 have a substituent as a non-ring atom bound to a ring atom of the aromatic ring structure adjacent to the ring atom bound to X 1 or X 2 ; and (b) none of R 3 to R 6 are aromatic with a ring atom of the aromatic ring structure bound to X 1 or X 2 with a polar substituent as a non-ring atom bound to a ring atom of the aromatic ring structure adjacent to the ring atom bound to X 1 or X 2 .
• X 1 and X 2 are independently selected from the group consisting of N and P, Preferably X 1 and X 2 are the same. Preferably both X 1 and X 2 are P.
• R 3 to R 6 may be a substituted hydrocarbyl group or a substituted heterohydrocarbyl group, that is at least one substituent is bound to the hydrocarbyl group or the heterohydrocarbyl group.
• substituted hydrocarbyl group or a substituted heterohydrocarbyl group that is at least one substituent is bound to the hydrocarbyl group or the heterohydrocarbyl group.
• substituted is as defined earlier, that is a substituent is a moiety (excluding H) which is bound to a linear structure or a cyclic structure bound to X 1 or X 2 , but does not form part of the linear or cyclic structure.
• the linear or cyclic structure may be selected from the group consisting of a linear hydrocarbyl, a cyclic hydrocarbyl and a cyclic heterohydrocarbyl group.
• Linear hydrocarbyl may include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl.
• Cyclic hydrocarbyl may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl cyclooctyl, cyclononyl, cyclodecyl, cyclopentenyl, cyclohexenyl, cyclo-octenyl, phenyl, cyclopentadienyl, naphthaleneyl, norbomyl, adamantyl, phenanthreneyl, anthraceneyl, phenaleneyl, tetrahydronaphthaleneyl, decalinyl, indenyl and tetrahydroindenyl.
• Cyclic heterohydrocarbyl may include tetrahydrofuranyl, tetrahydrothiopheneyl, pyrrolideneyl, piperidineyl, pyrrolineyl, oxazolyl, thiazolyl, furanyl, thiopheneyl, pyrazolinyl, pyrazolyl, imidazolyl, benzofuranyl, coumaranyl and indolyl.
• benzyl is considered to be methyl linear structure with a phenyl substituent and tolyl is considered as a phenyl cyclic structure with a methyl substituent.
• a group such as H 2 CIC - is, in terms of this specification considered to be a heterohydrocarbyl group and not a substituted hydrocarbyl group.
• R 3 to R 6 may also be selected from a group of metallocenes such as a ferroceneyl, zirconoceneyl and titanoceneyl group.
• R 3 to R 6 are the same or different and each is a hydrocarbyl group, or a heterohydrocarbyl group which contains no substituent or contains a non-polar substituent. Preferably each of R 3 to R 6 does not have any polar substituent. In one embodiment of the invention at least two of (but preferably all of) R 3 to R 6 are aromatic with a ring atom of the aromatic ring structure bound to X 1 or X 2 , but not more than two of said aromatic R 3 to R 6 having a non-polar substituent as a non-ring atom bound to a ring atom of the aromatic ring structure adjacent to the ring atom bound to X 1 or X 2 .
• aromatic R 3 to R 6 Preferably none of the aromatic R 3 to R 6 have a non-polar substituent as a non-ring atom bound to a ring atom of the aromatic ring structure adjacent to the ring atom bound to X 1 or X 2 .
• aromatic R 3 to R 6 are non-substituted aromatic compounds.
• R 3 to R 6 may be independently selected from the group consisting of a non-aromatic compound; an aromatic compound; and a heteroaromatic compound.
• each of R 3 to R 6 is an aromatic or heteroaromatic compound, more preferably an aromatic compound (including a substituted aromatic compound).
• the aromatic compound (or substituted aromatic compound) may comprise phenyl or a substituted phenyl.
• non-polar substituent is a substituent without a permanent electric or induced dipole moment.
• non-polar substituents include, but are not limited to, methyl, ethyl, ethenyl, propyl, iso-propyl, cyclopropyl, propenyl, propynyl, butyl, sec-butyl, tertiary-butyl, cyclobutyl, butenyl, butynyl, pentyl, isopentyl, neopentyl, cyclopentyl, pentenyl, pentynyl, hexyl, sec-hexyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyI, 2-isopropylcyclohexyl, cyclohexenyl, hexenyl, hexynyl, octyl, cyclo-octyl, cyclo-octenyl, decyl, benzyl,
• R 3 to R e may be independently linked to one or more of each other, or to Y to form a cyclic structure.
• R 3 to R 6 are the same or different and each is a hydrocarbyl group, or a heterohydrocarbyl group, provided that at least one of R 3 to R 6 contains a polar substituent on a carbon atom, but not one of R 3 to R 6 contains a polar substituent on a carbon atom of R 3 to R 6 adjacent to a carbon atom bound to X 1 or X 2 .
• One or more, or all of R 3 to R 6 may be independently selected from the group consisting of a substituted non-aromatic compound; a substituted aromatic compound; and a substituted heteroaromatic compound.
• each of R 3 to R 6 is a substituted aromatic or a substituted heteroaromatic compound, more preferably a substituted aromatic compound.
• the substituted aromatic compound may comprise a substituted phenyl.
• Any polar substituent on one or more of R 3 , R 4 , R 5 and R 6 may be electron donating.
• Suitable polar substituents may be a methoxy, ethoxy, isopropoxy, C 3 -C 20 alkoxy, phenoxy, methoxymethyl, methylthiomethyl, 1 ,3-oxazolyl, methoxymethoxy, hydroxyl, amino, pentafluorophenoxy, tosyl, methylsulfanyl, trimethylsiloxy, dimethylamino, sulphate, nitro or the like.
• R 3 and R 4 may be the same, and R and R 6 may be the same.
• R to R 6 may all be the same.
• Y may be selected from the group consisting of an organic linking group such as a hydrocarbyl, a substituted hydrocarbyl, a heterohydrocarbyl and a substituted heterohydrocarbyl; an inorganic linking group such as a single atom link (that is X 1 and X 2 are bound to the same atom); methylene; dimethylmethylene; 1 ,2- ethane; 1 ,2-ethene; 1 ,1 -cyclopropane; 1 ,1-cyclobutane; 1 ,1-cyclohexane; 1 ,1- cyclopentane; 1 ,2-cyclopentane; 1 ,2-cyclohexane; 1 ,2-phenylene; 1 ,8-naphthyl; 9,10-phenanthrene; 4,5-phenanthrene; 1 ,3-propane; 1 ,2-catechoI; 1,2- dialkylhydrazine; -B(R 7 )-,
• Y may be -N(R 7 )- and R 7 may be selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl groups or derivatives thereof, and aryl substituted with any of these substituents.
• R 7 may be a hydrocarbyl or a substituted hydrocarbyl group.
• R 7 may be methyl, ethyl, propyl, isopropyl, cyclopropyl, allyl, butyl, tertiary-butyl, sec-butyl, cyclobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclo-octyl, decyl, cyclodecyl, 1 ,5- dimetylheptyl, 2-naphthylethyl, 1-naphthylmethyl, adamantyl methyl, adamantyl, 2-isopropylcyclohexyl, 2,6-dimethylcyclohexyl, cyclododecyl, 2-methylcyciohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2-ethylcyclohexy
• Y may exclude (CH 2 ) X Z(CH 2 ) y , where Z is -P(R 8 )-, -N(R 8 )-, -As(R 8 )-, -Sb(R 8 )- or - S- and x and y are individually 1-15 and wherein R 8 is hydrogen or a halogen or a nitro group or a hydrocarbyl or a substituted hydrocarbyl group.
• Y may include a first atom bound to X 1 and a different atom bound to X 2 .
• Y includes or is a single atom bound to both X 1 and X 2 .
• the ligating compound is of the formula
• the ligating compound is a bidentate ligand.
• Non limiting examples of the ligating compound are
• (2-naphthyl) 2 PN(methyl)P(2-naphthyl)(phenyl); (2-naphthyl)(phenyl)PN(methyl)P(phenyl) 2 ;
• the ligating compound may include a polymeric moiety to render the reaction product of the source of transition metal and the said ligating compound to be soluble at higher temperatures and insoluble at lower temperatures e.g. 25°C.
• This approach may enable the recovery of the complex from the reaction mixture for reuse and has been used for other catalyst as described by D.E. Bergbreiter et al., J. Am. Chem. Soc, 1987, 109, 177-179.
• these transition metal catalysts can also be immobilised by binding the ligating compound to silica, silica gel, polysiloxane or alumina backbone as, for example, demonstrated by C. Yuanyin et ai, Chinese J. React. Pol., 1992, 1(2), 152-159 for immobilising platinum complexes.
• the ligating compound may include multiple ligating units or derivatives thereof.
• Non-limiting examples of such ligands include dendrimeric ligands as well as ligands where the individual ligating units are coupled either via one or more of the R groups or via the linking group Y. More specific, but not limiting, examples of such ligands may include 1 ,2-di-(N(P(phenyl) 2 ) 2 )-benzene, 1 ,4-di- (N(P(phenyl) 2 ) 2 )-benzene, N(CH 2 CH 2 N(P(phenyl) 2 ) 2 ) 3 , 1,4-di-
• the ligating compounds may be prepared using procedures known to one skilled in the art and procedures forming part of the state of the art.
• the tetramerisation catalyst may be prepared in situ, that is in the reaction mixture in which the oligomerisation reaction is to take place.
• Reaction mixture will be understood to include a reaction medium, reactants (olefinic compounds), reaction products and catalyst components.
• the oligomerisation catalyst will be prepared in situ. However it is foreseen that the catalyst may be pre-formed or partly pre-formed.
• the source of transition metal and ligating compound may be combined (in situ or ex situ) to provide any suitable molar ratio, preferably a transition metal to ligand compound molar ratio, from about 0.01 : 100 to 10 000 : 1, preferably from about 0.1 : 1 to 10:1.
• the process may also include combining one or more different sources of transition metal with one or more different ligating compounds.
• the tetramerisation catalyst or its individual components, in accordance with the invention, may also be immobilised by supporting it on a support material, for example, silica, alumina, MgCI 2 , zirconia, artificial hectorite or s ectorite clays such as LaponiteTM RD or mixtures thereof, or on a polymer, for example polyethylene, polypropylene, polystyrene, or poly(aminostyrene).
• the catalyst can be formed in situ in the presence of the support material, or the support can be pre-impregnated or premixed, simultaneously or sequentially, with one or more of the catalyst components or the oligomerisation catalyst.
• the support material can also act as a component of the activator. This approach would also facilitate the recovery of the catalyst from the reaction mixture for reuse.
• the catalyst may also include one or more activators.
• an activator may be a compound that generates an active catalyst when the activator is combined with the source of transition metal and the ligating compound.
• Suitable activators include aluminium compounds (including organoaluminium compounds), organoboron compounds, organic salts such as methyllithium and methylmagnesium bromide, inorganic acids and salts such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate, and the like.
• Suitable aluminium compounds include compounds of the formula AI(R 9 ) 3 (R 9 being the same or different), where each R 9 is independently a C C ⁇ 2 alkyl, an oxygen containing moiety or a halide, aluminoxanes, and compounds such as LiAIH 4 and the like.
• Aluminoxanes are well known in the art as typically oligomeric compounds which can be prepared by the controlled addition of water to an alkylaluminium compound, for example trimethylaluminium. Such compounds can be linear, cyclic, cages or mixtures thereof.
• organoaluminium activators include trimethylaluminium (TMA), triethylaluminium (TEA), tri-isobutylaluminium (TIBA), tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride, aluminium isopropoxide, ethylaluminiumsesquichloride, methylaluminiumsesquichloride, methylaluminoxane (MAO), ethylaluminoxane (EAO), isobutylaluminoxane (iBuAO), modified alkylaluminoxanes such as modified methylaluminoxane (MMAO) and mixture thereof.
• TMAO trimethylaluminium
• TEA triethylaluminium
• TIBA tri-isobutylaluminium
• methylaluminium dichloride e
• organoboron compounds examples include boroxines, NaBH 4l triethylborane, tris(pentafluorophenyl)borane, trityl tetrakis(pentafluorophenyl) borate, dimethylaniliumtetrakis(pentafluorophenyl) borate, tributyl borate and the like.
• the activator may also be or contain a compound that acts as a reducing or oxidising agent, such as sodium or zinc metal and the like, or hydrogen or oxygen and the like.
• the activator may be selected from alkylaluminoxanes such as methylaluminoxane (MAO), high stabilily methylaluminoxane (MAO HS), ethylaluminoxane (EAO), isobutylaluminoxane (iBuAO) well as modified alkylaluminoxanes such as modified methylaluminoxane (MMAO).
• alkylaluminoxanes such as methylaluminoxane (MAO), high stabilily methylaluminoxane (MAO HS), ethylaluminoxane (EAO), isobutylaluminoxane (iBuAO) well as modified alkylaluminoxanes such as modified methylaluminoxane (MMAO).
• Modified methylaluminoxane (a commercial product from Akzo-Nobel) contains modifier groups such as isobutyl or n-octyl groups, in addition to methyl groups.
• the transition metal source and the aluminoxane may be combined in proportions to provide Al/transition metal molar ratios from about 1 :1 to 10 000:1 , preferably from about 1 : 1 to 1000:1 , and more preferably from 1:1 to 500:1.
• the process may include the step of adding to the catalyst system a trialkylaluminium compound in amounts of between 0.01 to 1000 mol per mol of alkylaluminoxane.
• aluminoxanes generally also contain considerable quantities of the corresponding trialkylaluminium compounds used in their preparation. The presence of these trialkylaluminium compounds in aluminoxanes can be attributed to their incomplete hydrolysis with water. Any quantity of a trialkylaluminium compound quoted in this disclosure is additional to alkylaluminium compounds contained within the aluminoxanes.
• the further oligomerisation catalyst may comprise a conventional oligomerisation catalyst (e.g. as described in US 6555723, US 6683187 and US 20030144514), a dimerisation catalyst (e.g. as described in US 2003/0149198), but preferably it comprises a trimerisation catalyst.
• it comprises a trimerisation catalyst as described in any one of US 5811618, WO 02/04119, WO 03/053890, WO 03/053891 and PCT/ZA2003/000185, all of which are incorporated herein by reference.
• it comprises a catalyst as described in WO 03/053890 or PCT PCT/ZA2003/000185.
• Tetramerisation catalyst and further oligomerisation catalyst may comprise a conventional oligomerisation catalyst (e.g. as described in US 6555723, US 6683187 and US 20030144514), a dimerisation catalyst (e.g. as described in US 2003/0149198), but preferably it comprises a trim
• the further oligomerisation catalyst is a catalyst comprising the combination of i) a source of transition metal; and ii) a ligating compound, preferably of the formula
• a and C are independently selected from the group consisting of N, P, As, Sb, Bi, O, S and Se; B is a linking group between A and C; m' and n' are independently 0,1 or a larger integer; R' and R" are independently hydrogen, a hydrocarbyl group or a heterohydrocarbyl group; and R' being the same or different when n > 1 , and R" being the same or different when n 1.
• the oligomerisation catalyst is a trimerisation catalyst and the source of transition metal and ligating compound is as described in US 5811618, WO 02/04119, WO/053890 or WO 03/053891 or PCT/ZA2003/000185, all of which are incorporated herein by reference.
• the source of transition metal of the tetramerisation catalyst and the further oligomerisation catalyst as described above is the same source.
• it is a source of Cr in both cases.
• both the tetramerisation catalyst and the further oligomerisation catalyst may be prepared in the same medium (preferably in situ).
• the preparation may be carried out by combining i) a source of transition metal for both the tetramerisation catalyst and the further oligomerisation catalyst; ii) a ligating compound for the tetramerisation catalyst as defined above; iii) a different ligating compound for the oligomerisation (preferably trimerisation) catalyst; and iv) optionally an activator.
• the oligomerisation catalyst may be a trimerisation catalyst, and preferably it is as described in US 5811618, WO 02/04119, WO/053890 or WO 03/053891 or PCT/ZA2003/000185.
• an oligomerisation catalyst comprising the combination of i) source of transition metal for both a tetramerisation catalyst and a trimerisation catalyst; ii) a ligating compound for a tetramerisation catalyst as defined above; iii) a different ligating compound for a trimerisation catalyst; and iv) optionally an activator.
• the oligomeric product may include a mixture of at least one tetramer and at least one other oligomer.
• Both the at least one tetramer and the at least one other oligomer may comprise olefins or compounds including an olefinic moiety.
• the at least one tetramer may comprise octene, preferably 1-octene.
• the at least one other oligomer may comprise a trimer, preferably hexene, preferably 1-hexene.
• the at least one tetramer and the at least one other oligomer may be branched, but preferably they are non-branched.
• the at least one olefinic compound may comprise a single olefinic compound or mixture at olefinic compounds. In one embodiment of the invention it may comprise a single olefin.
• the at least one olefinic compound preferably comprises an olefin and the olefin may include multiple carbon-carbon double bonds, but preferably it comprises a single carbon-carbon double bond.
• the olefin may comprise an ⁇ -olefin with 2 to 30 carbon atoms, preferably 2 to 10 carbon atoms.
• the olefinic compound may be selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, styrene, 1-heptene, and 1-octene, 1-nonene, 1-decene, 3-methyl-1- butene, 3-methyl-1 -pentene, 4-methyl-1-pentene, p-methyl styrene, 1-dodecene or combinations thereof, Preferably it comprises ethene or propene, preferably ethene.
• the ethene may be used to produce octene (preferably 1-octene) and other oligomers, preferably hexene (preferably 1-hexene).
• the molar ratio of the tetrameristaion catalyst to the further oligomerisation catalyst may be 0.01 :1 to 100:1 , preferably 0.1 :1 to 10:1.
• the olefinic compound or mixture thereof to be oligomerised according to this invention can be introduced into the process in a continuous or batch fashion.
• the olefinic compound or mixture of olefinic compounds may be contacted with the oligomerisation catalysts at a pressure of 100 kPa or higher, preferably greater than 1000 kPa, more preferably greater than 3000 kPa.
• Preferred pressure ranges are from 1000 to 30000 kPa, more preferably from 3000 to 10000 kPa .
• the process may be carried out at temperatures from -100 °C to 250 °C. Temperatures in the range of 15-150 °C are preferred. Particularly preferred temperatures range from 40-120°C.
• the oligomerisation process may include the step of mixing the components of the catalysts at any temperature between -20 °C and 250 °C in the presence or absence of an olefinic compound or mixture thereof.
• the preferred temperature range being from 20 °C to 150 °C.
• the components of the catalysts may also be added separately and at different temperatures to allow for selective and controlled contact between the components.
• the individual components constituting the tetramerisation catalyst or further oligomerisation catalyst described herein may be combined simultaneously or sequentially in any order, and in the presence or absence of a solvent, in order to give an active and selective catalyst.
• the presence of an olefinic compound during the mixing of the catalyst components generally provides a protective effect which may result in improved catalyst performance.
• reaction products derived from the oligomerisation reaction as described herein may be prepared using the disclosed catalysts by a homogeneous liquid phase reaction in the presence or absence of an inert solvent, and/or by slurry reaction where the catalysts and the oligomeric product is in a form that displays little or no solubility, and/or a two-phase liquid/liquid reaction, and/or a bulk phase reaction in which neat reagent and/or product olefins serve as the dominant medium, and/or gas phase reaction, using conventional equipment and contacting techniques.
• the oligomerisation reaction may also be carried out in an inert solvent.
• Any inert solvent that does not react with the activator can be used.
• These inert solvents may include any saturated aliphatic and unsaturated aliphatic and aromatic hydrocarbon and halogenated hydrocarbon.
• Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, methylcyclohexane, methylcyclopentane, cyclohexane, Isopar C, ionic liquids as well as the product formed during the reaction in a liquid state and the like.
• the oligomerisation reaction may be carried out in a plant which includes reactor types known in the art.
• reactors include, but are not limited to, batch reactors, semi-batch reactors and continuous reactors.
• the plant may include, in combination a) a stirred or fluidised bed reactor system, b) at least one inlet line into this reactor for olefin reactant and the catalyst system, c) effluent lines from this reactor for oligomerisation reaction products, and d) at least one separator to separate the desired oligomerisation reaction products which may include a recycle loop for solvents and/or reactants and/or products which may also serve as temperature control mechanism.
• Example 1 Combined ethylene tetra- and trimerisation reaction using Cr(acetylacetonate) 3 , (phenyl) 2 PN('propyl)P(phenyl) 2 , (o- ethylphenyl) 2 PN(Me)P(o-ethylphenyl) 2 and MAO
• the mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 9.9 mmol) at 40°C.
• autoclave a 300 ml pressure reactor
• MAO methylaluminoxane, 9.9 mmol
• the pressure reactor was charged with ethylene after which the reactor temperature was controlled at 45°C, while the ethylene pressure was maintained at 4500 kPa.
• the reaction was terminated after 12 min by discontinuing the ethylene feed to the reactor and cooling the reactor to below 10°C. After releasing the excess ethylene from the autoclave, the liquid contained in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water.
• Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID.
• a small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID.
• the remainder of the organic layer was filtered to isolate the solid products. These solid products were dried overnight in an oven at 100°C and then weighed. The mass of total product was 111.66 g.
• the product distribution of this example is summarised in Table 1.
• Example 2 Combined ethylene tetra- and trimerisation reaction using Cr(acetylacetonate) 3 , (phenyI) 2 PN('propyl)P(phenyl) 2 , (o- ethylphenyl) 2 PN(Me)P(o-ethylphenyl) 2 and MAO
• the mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 4 mmol) at 40°C.
• the pressure reactor was charged with ethylene after which the reactor temperature was controlled at 45°C, while the ethylene pressure was maintained at 4500 kPa.
• the reaction was terminated after 13.5 min, and the procedure of Example 1 above was employed.
• the product mass was 68.58 g.
• the product distribution of this example is summarised in Table 1.
• Example 3 Combined ethylene tetra- and trimerisation reaction using Cr(acetylacetonate) 3 , (phenyl) 2 PN('propyl)P(phenyl) 2j (o- ethylphenyl) 2 PN(Me)P(o-ethylphenyl) 2 and MAO
• Example 4 Combined ethylene tetra- and trimerisation reaction using Cr(acetylacetonate) 3 , (phenyl) 2 PN('propyl)P(phenyl) 2 , (o- ethylphenyl) 2 PN(Me)P(o-ethylphenyl) 2 and MAO
• a solution of 3.2 mg of (phenyl) 2 PN( / propyl)P(phenyl) 2 (0.0075 mmol) (tetramerisation ligand) and 11.5 mg of (o-ethylphenyl) 2 PN(Me)P(o-ethylphenyl) 2 (0.0225 mmol) (trimerisation ligand) in 10 ml of toluene was added to a solution of 7 mg Cr(acetylacetonate) 3 (0.02 mmol) in 10 ml toluene in a Schlenk vessel.
• the mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80 ml) and MAO (methylaluminoxane, 4 mmol) at 40°C.
• the pressure reactor was charged with ethylene after which the reactor temperature was controlled at 45°C, while the ethylene pressure was maintained at 4500 kPa.
• the reaction was terminated after 19 min, and the procedure of Example 1 above was employed.
• the product mass was 99.05 g.
• the product distribution of this example is summarised in Table 1.
• Example 5 Combined ethylene tetra- and trimerisation reaction using Cr(acetylacetonate) 3 , (phenyl) 2 PN('propyl)P(phenyl) 2 , (o- ethylphenyl) 2 PN(Me)P(o-ethylphenyl) 2 and MAO
• the mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of methylcyclohexane (80 ml) and MAO (methylaluminoxane in toluene, 4 mmol) at 40°C.
• the pressure reactor was charged with ethylene after which the reactor temperature was controlled at 45°C, while the ethylene pressure was maintained at 4500 kPa.
• the reaction was terminated after 19 min, and the procedure of Example 1 above was employed.
• the product mass was 91.11 g.
• the product distribution of this example is summarised in Table 1.
• Example 6 Combined ethylene tetra- and trimerisation reaction using Cr(acetylacetonate) 3 , (phenyl) 2 PN('propyl)P(phenyl) 2 , (o- methoxyphenyl) 2 PN(Me)P(o-methoxyphenyl) 2 and MMAO
• MMAO-3A modified methylaluminoxane, 5.1 mmol was added and the mixture was immediately transferred to a 300 ml pressure reactor (autoclave) containing methylcyclohexane (80 ml) at 40°C.
• the pressure reactor was charged with ethylene after which the reactor temperature was controlled at 45°C, while the ethylene pressure was maintained at 4500 kPa.
• the reaction was terminated after 7 min, and the procedure of Example 1 above was employed.
• the product mass was 84.2 g.
• the product distribution of this example is summarised in Table 1.
• Example 7 Combined ethylene tetra- and trimerisation reaction using Cr(acetylacetonate) 3 , (p-methoxyphenyl) 2 PN(Me)P(p-methoxyphenyl) 2 , (o- ethylphenyl) 2 PN(Me)P(o-ethylphenyl) 2 and MMAO
• MMAO-3A modified methylaluminoxane, 1.3 mmol was added and the mixture was immediately transferred to a 300 ml pressure reactor (autoclave) containing methylcyclohexane (90 ml) at 40°C.
• the pressure reactor was charged with ethylene after which the reactor temperature was controlled at 45°C, while the ethylene pressure was maintained at 4500 kPa.
• the reaction was terminated after 23 min, and the procedure of Example 1 above was employed.
• the product mass was 47.9 g.
• the product distribution of this example is summarised in Table 1.
• Example 8 Combined ethylene tetra- and trimerisation reaction using Cr(acetylacetonate) 3 , Ph 2 PN(Me)N(Me)PPh 2 , (o-ethylphenyl) 2 PN(Me)P(o- ethylphenyl) 2 and MMAO
• MMAO-3A modified methylaluminoxane, 2.5 mmol was added and the mixture was immediately transferred to a 300 ml pressure reactor (autoclave) containing methylcyclohexane (80 ml) at 40°C.
• the pressure reactor was charged with ethylene after which the reactor temperature was controlled at 45°C, while the ethylene pressure was maintained at 4500 kPa.
• the reaction was terminated after 5 min, and the procedure of Example 1 above was employed.
• the product mass was 52.47 g.
• the product distribution of this example is summarised in Table 1.
• Example 9 Combined ethylene tetra- and oligomerisation reaction using Cr(acetylacetonate) 3 , (phenyl) 2 PN('propyl)P(phenyl) 2 , Fe-bisiminopyridyl (U and MMAO
• the pressure reactor was charged with ethylene after which the reactor temperature was controlled at 45°C, while the ethylene pressure was maintained at 3000 kPa. The reaction was terminated after 30 min, and the procedure of Example 1 above was employed. The product mass was 34.6 g.
• the product distribution of this example is summarised in Table 2.
• Example 10 Ethylene oligomerisation reaction using Fe-bisiminopyridyl (1) and MMAO (comparative example)
• Percentages are expressed as weight % (of total product).

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